Cathodic reduction of pyridine in liquid ammonia

✍ Scribed by O.R. Brown; R.J. Butterfield; J.P. Millington

• Publisher: Elsevier Science
• Year: 1982
• Tongue: English
• Weight: 801 KB
• Volume: 27
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(82)80094-7

✦ Synopsis

In liquid ammonia at -4O", pyridines give a single reduction peak corresponding to the formation of the radical anion. Alternative electrochemical kinetic techniques have been used to determine rate constants for the dimerisation of the radical anions. The chemical stability of the resulting dimeric dianion has bean examined and the kinetics of its anodic oxidation investigated. The mechanism of the oxidation of the same species by molecular oxygen is discussed. The reaction of the dianions with alkyl halides differs in the cases of pyridine and 4-methylpyridine, the latter giving the N,N'-dialkyl derivative but pyridine yielding only polymer. Pyridine radical anions react with alkyl bromides only in a simple charge transfer reaction.